Yarn conditioning process and composition therefor



Patented June 1942 UNITE STATES PATENT OFFICE YARN CONDITIONING raocnssAND COMPOSITION 'rnnanron Joseph B. Dickey and James G. McNally,Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., acorporation of New Jersey No Drawing. Application February 24, 1940,

. Serial No. 320,718

3 Claims.

manufacture, processing and use of yarns com-.-

posed of or containing organic derivatives of cellulose and similarsynthetic materials give rise to numerous problems generally absent fromthe handling of natural yarns such as silk, wool, cotton and the like.One of the chief problems en-. countered in dealing with these syntheticmate- 'rials is to so lubricate or soften and, in some inthe yarn overrolls, guides, and other parts of the yarn-producing mechanism and .intwisting,

winding, reeling and similar operations. In the caseof yarnsintended'for use on commercial knitting machinery, it is particularlyimportant that the yarn be soft and pliable inorder that 'it'mayconformto the contour 'of'the needles and give a closely knit fabric free fromcuts, pin holes, stitch distortion, laddering, misplaits and othercommon defects. 7

'Another problem of major proportions presented by thesesynthetic yarnsis their extreme tendency to pick up charges of static electricity,especially 'in such operations as twisting, winding, warping-picking,carding, combing, drafting, spinning, and thelike. This tendency isparticularly aggravated in the case of cut staple fibers, since in thecommercial use of such material it is normally subjected to a number ofextremely severe operations such as picking, carding, combing, etc., allof which tend to so charge the individual fibers as to make proper webformation diflicult or impossible or togive the ultimate yarn anundesirable'unevenness.

In some types of yarn, all three of the abovementioned problems oflubrication, softenlng'and anti-static treatment are present and'in anycase the matter of providing a yarn conditioning composition, in whichthe several functions are properl'y coordinated to accomplish thedesired result is often a matter of extreme difiiculty. This is due tothe fact that in any given yarn conditioning composition, whetherprimarily designed for use a a warp, filling or knitting lubricant, oras an anti-static, all of the various components and their functionsmust be delicately balanced one against the other so as to give apractical and commercially satisfactory yarn treatment.

Heretofore, many different conditioning agents such as pclyhydricalcohols and similar compounds have been suggested as ingredients ofyarn conditioning formulas, generally in. conjunction with mineral,vegetable and animal oils.

It has been found in practice, however, that most of these agents andthe various formulas containing them have certain drawbacks, among whichmaybe mentioned too drastic solvent action on the yarn, insuificientsolvent power for the lubricants with which they are used and a tendencyto form gummy deposits on the yarn after application. Furthermore, manyof the known lubricating, softening and anti-static agents areinsufliciently soluble in water to permit satisfactory removal from theyarn by aqueous scour baths.

The present invention has as its principal object to provide an improvedprocess for the conditioning of textile yarns, threads, filamentsyandfibers, particularly those composed of or containing organic derivativesof cellulose to render such materials amenable to various textileoperations and processes, such as knitting, weaving, spinning and thelike. A further object is to provide an improved process for thelubrication, softening and anti-static treatment of such yarn. A

'still further object is to provide a new class of posed-of orcontaining organic derivatives of cellulose and readily removabletherefrom by the,

usual aqueous scourbaths. A specific object is I to provide an improvedtype of cellulose organic derivative cut staple fiber amenable to.carding,

-drawing, spinning; and. other' processi'ng steps customarily employedin the manufacture of spun yarn onthe woolen, worsted, and cotton sys--tems. Other objects will appear hereinafter.

These objects are accomplished by the following invention which, in, itsbroader aspects, comprises treating yarns, particularly those composedof or containing organicderivatives of cellulose,

' such as cellulose acetate, cellulose acetate pro pionate, celluloseacetate butyrateand similar organic acid esters with thephosphinous andphosphinic acids, especially thosederived from aldehydes and ketones ofthe type represented by the formula: I 1 fRA -R where Ris a substituentselected from the group consisting of the alkyl and naphthenyl radicalsand R is a substituent selected from the group consistin'gof the alkyl,aryl, naphthenyl radicals "and hydrogen, and the inorganic and organicbase salts of these acids.

The phosphinous acids may the structural formula:

represented be represented by wherein R and B have the same meaning asindicated in the previous paragraph. The arkyl group may be any groupsuch as methyl, ethyl, propyl, butyl, amyl, or, in fact, any alkylgroup, even including alkyl groups of26 or more'carbon atoms. The arylsubstituent may likewise be any aryl group such as benzene, biphenyl,naphthalene, furan, thiophene, carbazole, anthracene, acenaphthene,fluorene, phenanthrene. By the term naphthenyP' we refer to radicals ofthe general class described in Chapter 48 of the Chemistry of PetroleumDerivatives by Carlton Ellis.

The salts in question may be prepared by the interaction of the acidswith any desired inorganic base such as sodium hydroxide, potassiumhydroxide, calcium hydroxide, ammonium hy-- droxide, or with any organicbase such as ethanolamine, diethanolamine, triethanolamine,triethylamine, ,butylamine, dibutylamine, tributylamine,tetrahydrofurfurylamine, ditetra hydrofurfurylamine,tritetrahydrofurfurylamine,

amyl amine, cyclohexylamine, dicyclohexylamine, diethylcyclohexylamine,dimethyl cyclohexylamine, beta-hydroxyethyl cyclohexylamine, di betahydroxyethylcyclohexylamine, glucose amine, ethylene diamine,tetramethyl ammonium hydroxide, trlmethyl benzyl ammonium hydroxide andthe like.

Under the broad class of phosphinous and be more fully describedhereinafter, have a peculiar ability to lubricate and soften such yarnsand at the same time give them anti-static properties. They also possessan unusual solvent power for mineral, blown and unblown, drying andsemi-drying vegetable and animal oils, and accordingly may be used withor without such oils. These compounds are further characterized by theirexceptional ability to reduce static charges on cellulose organicderivative cut staple fiber and thus to adapt them for carding, drawing,spinning and other operations customarily employed in the manufacture ofspun yarn on the woolen, worsted, and cotton systems. The yarnconditioning agents of our invention also have exceptional value assurface-active compounds and as such may be employed as wetting,dispersing, and emulsifying agents, textile 75 as follows:

assistants, dye dispersing agents and the lik These agents may also beused 'as substitutes for soaps because of their exceptionalemulsifyingpower. These compounds are characterized by their stability to hardwater and the fact that The phosphinous and phosphinic acids in generalmay be prepared in accordance with the method described in Friend'sTextbook of Inorganic Chemistry, vol. 11, part 3, chapter 1. The saltsof these acids may be prepared by the interaction of any inorganic ororganic base with the acids in question in accordance with knowntechnique and need not be described in detail here. I

A compound which we have found to be particularly valuable for thepurposes of our invention is 2-hydroxyheptane phosphinate-2 CH:CC5H11P.-OH I (")\0H This compound may be prepared as follows:

150.7 g. (1.1 moles) of phosphorous trichloride is added with stirringto 114 g. of methyl namyl' ketone, keeping the temperature at 30-35" (15minutes). The reaction mixture is allowed to stand overnight and thenadded with stirring to 600 cc. of glacial acetic acid, and thetemperature is kept at 30. After standing overnight the acetyl chlorideis distilled OE and the acetic acid is removed under reduced pressure.The product is poured intowater and washed with water until free ofmineral acid. From this acid, any desired salt, such as the sodium,ammonium, trithanolamine, diethylcyclohexyl, etc., may be prepared.Similarly, the phosphinic acid from ethyl-n-amyl ketone, methyl n butylketone, dibutyl ketone, methylpentadecyl ketone, methylheptadecylketone, etc., may be prepared.

Hrnaoxr ALKYI. ABYL Pnosrrrma'ras These compounds may be prepared inaccordance with the method described by Conant, Journal of the AmericanChemical Society, vol. 43, page 1928 (1921); Ibid 44, 2530 (1922).Falling within this broad class of compounds, we have prepared and foundespecially useful as anti-static agents in the treatment of yarns andcut staple fibers composed of cellulose acetate and other celluloseorganic derivatives, 8. new series of phosphinic acid compounds havingthe general formula:

wherein R is a substituted or unsubstituted aromatic group, R is analkyl group containing atleast five carbon atoms, and b is a small wholenumber up to 4. The aromatic group may be substituted by a radical orgroup such as alkyl, aryl, alkow, alkylamino, hydroxy, carboxyl, and thesulfonic acid group. The alkyl group may a; methyl, ethyl, propyl,butyl, amyl, and the A typical compound of this type, phenyl'amylhydroxy methane phosphinate, may be prepared 'keeping the temperaturebetween 2030. reaction mixture is allowed to stand 12 hours and To 162'g. phenyl amyl ketone are added slowly with stirring 152 g. phosphorustrichloride, keeping the temperature below 35. The mixture is allowed tostand one hour and about 200 g. acetic acid are added with stirring andcooling, The

then 50-60 g. ice are added. The mixture is then evaporated slowly on asteam bath. If the product crystallizes, it is filtered, washed withacetic acid, and dried. If the product separates as an oil, it isdissolved in a suitable solvent, such as ether, chloroform, etc., andwashed with water to remove acetic and mineral acids. The product may beregarded as phenyl amyl hydroxy methane phosphinate and has thestructural formula:

mineral acid.

The preparation of the diethyl cyclohexylamine salt of phosphinatedstearyl-palmityl xylyl ketone and similar compounds we have found to beespecially efficacious as textile anti-static is illustrated by'thefollowing procedures:-

169 g. of phosphorous trichloride is added to a mixture of ketones (310g.) prepared from mixed xylenes and a mixture of stearic and palmiticacids heated to 60. The mixture is heated to 60-70 with stirring foreight hours and then for 12 hours at room temperature. Then 240 g. ofacetic acid is added and warmed to 60-70 for 8 hours. The acetylchloride and acetic acid are removed, the product is poured into waterand washed free of mineral acid. The resulting heavy, oily acid may betreated with any desired base to form a salt. Thediethylcyclohexylaminesalt, for example, may be considered to be amixture of stearyland palmityl xylyl ketones. These compounds may berepresented by the following structural formulae:

Mixture of OH I g (I C1sHa1 (C O H'diethylcycloheXylamine OH (I /C17H:so=r-oH-diem le clohex lamin- Preparation of a similar compound may becarried out as follows: I

169 g. of phosphorous trichloride is added to a mixture of ketones (275g.), prepared from a mixture of myristic and capryllc acids and mixeddiethyl benzenes, heated to The mixture is heated to 60-70 with stirringfor 8 hours and then for 12 hours at room temperature. Then 240 g. ofacetic acid is added and the reaction mixture is warmed to 60-70 for 8hours. The acetyl chloride and acetic acid are distilled over and theproduct is poured into water and washed free of mineral acids. Salts areprepared by reacting the acid with one or two equivalents of the desiredbase. More than one basemay be used to give a mixture of salts.

Examples of suitable bases for the preparation of the salts are sodiumhydroxide, potassium hydroxide, ammonia, triethylamine, pyridine,morpholine, ethylene diamine, dibutylamine, amylamine, tetramethylammonium hydroxide, triethylbenzylammonium hydroxide, mono, diandtri-ethanolamine, ethyl cyclohexylamine, diethylcyclohexylamine,dimethylcyclohexylamine, di-beta-hydroxyethylcyclohexylamine,dicyclohexylamine, diand tri-tetrahydrofurfurylamine, etc.

In a similar manner may be prepared the following illustrativecompounds.

(Phenyl amyl hydroxymethane phosphinate) 0H -CqHw (Phenylnonyl hydroxymethane phosphinate) (Mixed xylyl undecyl hydroxy methane phosphinate)in GC15Ha| I 0\ O= P=(0H)1 alkyl (Ortho. meta or para phenyl alkoxypentadecyl hydroxy methane phosphinate) 11 |JC11Has O= P=(OH)2 SOaH(Ortho, meta or para sulfophenyl heptadecyl hydroxy methane phosphinate)0: =(0H) 2 (Para xenyl heptadecenyl hydroxy methane phosphinate) l- 1531 O= i'=(OH) 2 v (Alpha naphthyl pentadecyl hydroxy methanephosphinate) (Para-dialkylamino phenyl hexahydrobenzyl hydroxy methanephosphinate) wherein R is a substituent selected from the Hg t cH, Cc.H, group consisting of alkyl, alkylene, aryl, heterocyclic andcycloaikyl groups,--with phosphorus O OH trichloride, an organic acidand then with water. (on): 5 The resulting compounds may be represented.by. (Fur-fury] bntyl hydroxy methane phosphinate) the structural a; on tOH. HO 47-0511 R-l-naphthenyl o: i 0 on), H C i um) g g I BHil wherein Ris a substituent selected from the (Hydroxy phenyi-2,4 bis amylhydroxy-methane phosphlnate) group consisting of alkyl, alkylene, aryl,,heteru- CHr-CH, l5 cyclic and cycloalkyl groups and Z is hydrogen OH ora salt-forming group. By salt-forming group 0311,) M g p we mean anyorganic or inorganic compound I I-CsHu having basic properties such asthose referredmore 0=P=(0H)z to in the preparation of the compoundsgiven above. By the term naphthenyl," we'refer to gg g gg prowlwenaphthenyl my! hydww methane radicals of the same class described inchapter 48 of Ellis textbook The Chemistry of Petro- HC=CH leumDerivatives 1934 edition. I

I The aliwl and similar ketones required for thepreparation of thesecompounds may be obtained as disclosed in U. S. Patents 1,989,325 and1,988,021. The aryl naphthenyl ketones may be prepared by reactingcertain aromatic hydrocar bons such as benzene, naphthalene. diphenyl,triphenyl, anthracene, dibenzofuran, furan; thiophene, acenaphthene,etc. in substituted or unsubstituted iorm with naphthenic acid chlorideprepared by reacting naphthenic acid or a mixture of naphthenic acidswith an acid chloride- (Dihenzo fur-an amylhydroxy methane phosphinicacid) forming reagent such as thionyl chloride phos H phorouspentachloride, phosphorous trichloride,

, oxalyl chloride, benzoyl chloride, etc. This procedure is set forth inour copending application Ser. No. 290,320, filed August 15, 1939.

N o: 40 The preparation of a typical naphthenyl phos- H phinic acid suchas phenyl naphthenyl hydroxy r z amyl hydr yeth n ph sn methanephosphinic acid may be carried out as 0H follows: v One mole of ==(0H),OC-naphthenyi r b):

'1"-i 1n lhtd lhdr m h mm n some p my ep 8 many y on me mp n8 is addedto 160 g. phosphorous trichloride (10% OH excess) at 35. After threehours add 600 cc.

ocH acetic acid at such a rate that the temperature O==(OH), remainsbetween 20-30. The reaction mixture 0.11.). is allowed to stand 12 hoursand poured onto ice (Tetrabutyl phenyl pentacosane hydroxy methanephosphinate) (600 and the mixture allowed to evaporate on a steam bathuntil the reaction product has E crystallized. The product is phenylnaphthenyl -ciH" hydroxy methane phosphinic acid and has the CNH J:structural formula I Ha): I .QC-naphthenyi (Decyl dimethyl phenyiamyl-hydroxymethane phosphinate) v i orr -$-CIH1I E 0: lPzwml Thepreparation of another typical compound, can CH; methyl naphthenylhydroxymethane phosphinic (Isopropyi methyl phenyi nonyl hydroxy methanephosphinate) acid may be carried as follows:

. One mole or NAPHTHENYL Pnosrrnmc ACIDS AND THEIR Sam's Thesecompounds, which so far as we are aware, are new chemical compounds, maybe pretin k t m havm the eneml is added to 160 g. (10% excess)phosphorus tng iffi reac g e o S. g g chloride at 35. After three hoursthe complex is added to 600 cc. acetic acid maintaining a temperature of20- -30. The reaction mixture is al- R--haphthenyl lowed to stand 12hours, poured onto ice (600g) 0 Ha-("f-naphthenyl and the mixture isevaporated on a steam bath until no further crystallization takes place.The crystals are filtered off and dried. .The product is methylnaphthenyl hydroxy methane phosphinic acid and has the formula:

Likewise the following compounds may be prepared:

I NaphthenylC-naphthenyi o= r= oH), (Dinaphthenyl hydroxy methanephosphinate) SOaH I cay1oOonaphmeny1 (p-cetoxy m-sulio phenyl naphthenylhydroxy methanephosphinatc) Hz-C 0 H2 OH CH; CH-C-naphthenyl 1 0 0:P:(OH):

(alpha-tetrahydrofuryl naphthenyl hydroxy ethane phosphinate) HO CzHs NCHzCH Cnaphtheny1 CzHs )H (3-diethylamino-l,l,l hydroxy-naphthenylpropane phosphinate) (alpha-pyridyi naphthenyl hydroxy methanephosphinate) OH CzHs-(J-naphthenyl 0: P O K 0 K V (ethylnaphthenylhydroxy methane phcsphinate dipotassium salt) 0H CIHI- k-naphthenyl O NaO H-NHz- C 2H4 O H (naphthenyl butyl hydroxy methane phosphinateethanolamine (p-phenyi phenyl naphthenyl-hydroxy methane phosphinate)Another typical compound, the diethylcyclohexylamine salt ofphosphinated naphthenyl xylyl ketone may be prepared as follows:

g. of phosphorous trichloride is added with stirring to naphthenyl xylylketone (300 g.) heated to 60. Heating and stirring are continued at60-70" for 8 hours. The reaction mixture is allowed to stand at roomtemperature for 12 hours and then 240 g. of acetic acid is added. Themixture is heated with stirring at 60-70 for 8 hours and the acetylchloride and excess acetic acid are removed by distillation. The productis poured into water and washed free of mineral acids, separated, driedby evacuation, and then treated with one molecular equivalent of diethylcyclohexylamine. The product is the diethylcyclohexylamine salt ofphosphinated naphthenyl ketone and has the following for-P-OH.diethylcyclohcxylamine 2): 0

Likewise, the preparation of the diethylcyclohexylamine salt ofphosphinated dinaphthenyl hydroxy methane may be prepared as follows:

1'70 g. of phosphorous trichloride is added with stirring to 300 g. ofdinaphthenyl ketone heated to 60. After heating at 60-70 for 8 hours thereaction mixture is allowed to stand at room temperature for 12 hours.Then 240 g. of acetic acid is added and the mixture is heated at 60-70"for 8 hours. The acetyl chloride and excess acetic acid are removed andthe product is poured into water. After washing free from mineral acid,the reaction product is reacted with diethylcyclohexylamine. Theresulting' compound, diethylcyclohexylamine salt of phosphinateddinaphthenyl hydroxy methane has the structural formula 0H naphthenyl(3-naphthenyl O= 0H.diethylcyclohexy1amine In a. similar manner, anydesired salt may be prepared.

As indicated by the above examples, the salts of any of these compoundsare prepared by treat- I Cnaphthenyl H) II (alpha-naphthyl naphthenylhydroxy methane phosphinate) 170 g. phosphorous trichloride is addedwith stirring to 350 g. naphthenyl-alpha-naphthylketone at 60. Heatingand stirring are continued at 6070 for 8 hours. After standing for 12hrs. 240 g. acetic acid are added. The mixture is heated with stirringfor 8 hours and then the acetic acid and acetyl chloride are distilledoff. The product is poured into water and washed free of mineral acid.The product is a heavy, viscous oil. In a similar manner thecorresponding beta acid is prepared Similarly, acenaphthenyl naphthenylhydroxy methane phosphinat may be prepared.

CHz-CH:

0 H (J-naphthenyl 'o= P-OH 0H (acenaphthenyl naphthenyl hydroxy methanephosphinate) 170 g. phosphorous trichloride is added with stirring to360 g. acenaphthenyl naphthenyl ketone heated to 60. Heating andstirring are continued at 60-70 for 8 hours. After standing for 12 hours240 g. acetic acid is added. The mixture is heated with stirring for 8hours and the acetic acid and acetyl chloride are distilled 011. Theproduct is poured into water and worked free of mineral acid. Theproduct is a heavy, viscous oil.

In like manner the following compounds may b prepared:

(Anthraeene naphthenyl hydroxy methane phosphinate) B-mphmeny1 (5 61am.

(Phenanthrene naphthenyl hydroxy methane phosphinate) OH I 3-naphthenyl0nn (Dibenzoluran naphthenyl hydroxy methane phosphinate) JICH 0(Benzoiurane naphthenyl hydroxy methane phosphinate) i ---(|J-naphthenylg/V O='P=(OH),

Carbazole naphthenyl hydroxy methane phosphinate) naphthenyl OH N O: P=(0 H), H

(S-hydroxy quinolyl naphthenyl hydroxy methane phosphinate) C-(naphthenyl) (naphthalene (bis-naphthenyl hydroxy methane phosphinate))Any of the compounds previously described may be sulfonated in the arylgroup by warming with sulfuric acid or chloro-sulfonic acid.

In the following examples and description we have set forth several ofthe preferred embodiments of our invention, but they are included merelyfor purposes of illustration and not as a limitation thereof.

Our invention will be more readily understood by reference to severalspecific examples of typical yarn treating procedures carried out inaccordance therewith.

USE or PHOSPHINOUS AND Pnosrnmro Aorns AND Tnam SALTS AS YARNConm'rromuo AGENTS Example 1 OH O l C H;;C- P- 0H.diethanolam1ne salt(l-hydroxy-octadecane phosphinate-l diethanolamine salt) is applied bymeans of an applicator roll to cellulose acetate continuous filamentdesigned forknitting purposes in an amount corresponding to 5-25% of thedry weight of the yarn. The yarn so treated is found to be soft andpliable and well-adapted for knitting.

Example 2 A conditioning liq'uid having the following composition: -95parts by weight butyl naphthenate 10-5 parts (hHn-C- P.diethylcyclohexylamine salt H 0-H (l-hydroxy dodecane phosphiiigte-ldiethylcyclohexylaminc is applied to a cellulose acetate cut staplefiber designed for use on the woolen system in an amount correspondingto 1-5% of the dry weight of the staple fiber material. The yarn sotreated Y is found to be substantially free from accumulations of staticelectricity and admirably adapted for the manufacture of spun yarn inaccordance .with standard commercial practice involving carding,drawing, spinning and the like.

Other examples of conditioning compositions which may be applied inaccordance with our in- (l-hydroxyhexadecane phosphinous acid amylaminesalt) 99-90 parts mineral oil Example 4 10 parts butyl naphthenate 89-80parts mineral oil 1-10 parts 11 7 C17HQQC-POH,NHQC1QH35 H 0 OH(l-hydroxy octadecene amine salt) phosphinate-l-oleyl- Example 99-90parts blown olive oil 1-10 parts C H3-CCH' P .dietbylcyclohexylamlnesalt 0 ()H OH (a-hydroxy-p-keto propyl-a-phosphinousdiethylcyclohexylamine salt) Example 6 80-99 parts olive oil 20-1 partsacid H V (0 Ha) zC- 0- 8 GHxdiamylamine salt(3-hydroxy-2-keto-isohexane-3-phosphinate diamylamine salt) Example 710-1 parts 0 C H 1( 3-C H3.tetrabydroiuriurylamine salt(Z-hydroxy-heptane phosphinate tetrabydroiurfurylamine salt) 90-99 partsneats-foot oil Example 8 -1 parts Giza-0H, 0H CH2 CHI-Cg] P.dioleylamine salt H (l-hydroxy-cyclohexane phosphinate-l-(lioleylaminesalt) 80-99 parts blown neats-foot oil Example 9 55 parts sperm oil 5parts CmH33-- P .NHz-C:H4O C2Hl 0 CiHs (Hexadeeano phosphinate-lB-ethoxy-flethoxy ethylamiue salt) 20 parts'butyl naphthenate 20 partsmineral oil Example 10 77-68 parts blown sperm oil 1-10 parts(l-hydroxy-l-phenyl octadecene phosphinate-l potassium salt) 2 partswater 20 parts ,B-di-methoxy ethyl succinate Example 11 1-10 parts CH:CHCCHz-C o P- 0N8 H (l tetrahydroiuryl-l-hydroxy propane-ii-phenylats-K-sodium salt) phenoxy phospbin- 99-90 parts teaseed oil Example 1260-70 parts glyce'rolacetone acetate 39-20 parts blown teaseed oil -10parts (1-Hydroxy-l-phenyl-Il-ketobutane butoxy phospbinato sodium salt)Example 1 3 1-10 parts a O CaHii C|Hw P .dietliylcyclohexylamine salt 0H g\ 0 H (l-Hfiiroxy pentane pentoxy phospbinate diethylclyclohexylamine30 parts blown olive oil 69-60 parts blown neats-foot oil Example 1455-50 parts olive oil 10 parts sulfonated castoroil 20 parts mineral oil10-15 parts oleic acid 5 parts I OH 0 aHa P .morphcliue salt (Dodecanepbosphinous acid morpholine salt) YARN CONDITIONING AGENTS This class ofcompounds may be used in ac- Example 17 Per cent Mineral oil 55Diethylcyclohexylamine salt of phosphinated stearyl-palmityl xylylketone 36 Pine oil 9 Example 18 Per cent Mineral oil 64'Diethylcyclohexylamine salt of phosphinated stearyl-palmityl xylylketone 36 Example 19 Per cent Sodium potassium ethyl phosphate 35 sMineral nil 40 Terpene ether (produced by theaction of ethylene oxide onterpineol) V 7.5 Oleic acid 7.5 Monoethanolamine 7.5Diethylcyclohexylamine salt of phosphinated stearyl-palmityl xylylketone I 2.5

Example Per cent Mineral nil 44 Sperm oil 16 Diethylcyclohexylamine saltof phosphinated stearyl-palfnityl xylyl ketone 20 Terpene ether(produced by the action of ethylene oxide on terpineol) 10Triethanolamine oleate 10 Examples of compositions adapted for theconditioning of continuous filament yarns are the Examples Example 15Example 22 r 70 parts water 15 partswater soluble cellulose ester gg 3"""'v" 5 ri CH Oleic a i 9 Y I 5 Sulphonated olive oil 11 W -fiPotassium olea 1 0H 0 on Diethylcyclohexylamine salt of phosphinated vHa stearyl-palmityl xylyl ketone 4 (2-Hydroxy heptadecane pbosphinicacid oetylamlne salt) 10 P 23 10 parts sulfonated olive oil Mineral nilPine oil I 10 10 parts Example 16 Diethylcyclohexylamine salt ofphosphinated v stearyl-palmityl xylyl ketone 20 I V Triethanolamineoleate 10 naphthenyl-0-naphthenyl v I 0,=P- 0Ediethylcyclohexylaminesalt Example 24 I Sulphonated olive oil 12 Y t Sul honated 'castor oil'7 (Dinaphthenyl hydroxy methane phosphmate 20 potgssium 018a, 3 Vdiethyl cyclohexylamine salt) Mineral Oil 53 20 parts mineral oil Oleicacid 5 70 Parts blown Olive 011 Diethylcyclohexylamine salt ofphosphinated Usn or HYDBOXY ALKYL ABYL PHOSPHINATES AS y -p yl xylylketone ..t. 20

USE or NAPHTHENYL PHOSPHINIO AcIDs AND Tnnnr Example 25 OH ICzHa-JJ-naphthenyl -OH.dlcthanolamine 0H (ethlyg naphthenyl hydroxymethane phosphinate diethanolamine is applied by means of an applicatorroll to cellulose acetate continuous filament designed for knittingpurposes in an amount corresponding to 5-25% of the dry weight of theyarn. The yarn so treated is found to be soft and pliable andwell-adapted for knitting.

0 0=P OH H \0 B:.diethylcyelohexylamima salt '(dlnaphthcnyl hydroxymethane phosphinate diethyl cyclohexylamine salt) is applied to acellulose acetate cut staple fiber designed for use on the woolen systemin an amount corresponding to 1-5% of the dry weight of the staple fibermaterial. The yarn so treated is found to be substantially free fromaccumulations of static electricity and admirably adapted for themanufacture of spun yarn in accordance with standard commercal practiceinvolving carding, drawing, spinning and the like.

Additional examples of conditioning compositions containing this classof compounds which may be applied in accordance with our invention toyarns intended for a variety of purposes such as knitting, weaving,spinning and the like, and especially the anti-static treatment of cutstaple fibers and other yarns composed of or containing organicderivatives of cellulose, such as cellu- Example 34 lose acetate,cellulose acetate propionate, and cellulose acetate butyrate and similarderivatives are the following: i Y

68 parts blown sperm oil 10 parts (J11 i 37 C5H |Cnaphthenyl 1 1o parts0H 0=P-0H.cyclohexylamine V 4 0H.tetramethylammomum hydroxide (Amylnaphthenyl hydroxy methane hosphinate cyclo- P.ONa hexylaminetetramethyl ammonium ydroxide salt) CHa(Poly) g\ OILdxtm-furylamme 2parts water (ngfihtllenfil (mixed)1xylyl hydroxy methane phosphinatesodium parts beta'dl'methoxyethyl Succmate t v mm Example35 99-90 parts0 ve 011 15 parts Example-28 1-20 parts H (I?%H HC\ /CC" nabhthenyl 2oEqf 0 -orr v H E I c-mbutylamme o 0H.dimethylanilin (Furyl naphthenylhydroxy methane phosphinate tributylamine 1 I salt) (Naphthenyltetrahydronaphthalene hydroxy methane bhosbhinate 99-80 parts blownolive O11 potassium dimethylamline salt) Example 29 99-90 parts teaseedoil Parts Example 36 I 38-20 parts blown teaseed 011 naphthenylC-naphthenyl 60-70 parts glycerolac'etone acetate 0:P-OH.diethylcyclohexylamine 2-10 parts v O H.butylaminenaphthenyl-(E-nabhthenfl @(Dmaphthenyl-hydroxy methane phosphinatediethylcyclohexyl- OH amine, butylamine salt) P30 99-90 parts numeral011 (OH)adiethylcyclohexylamine Example 30 (Dinaphthenyl hydroxy methanephosphinate diethylcy'clohexylamine salt) 7 10 parts butylstearate .1Example 37 89-80 parts mineral 011 40 1-10 parts 1-10 parts OH OH I vnaphthenyl C4Hu(l3naphthenyl o O =P= d'thl clh 1 me 0=P=(OH)z.oleylamlnew my (Phenyl naphthenyl hydroxy methane phosphinate diethylcyclo- (Butylnaphthenyl hydroxy methane phosphmate oleylamlne salt) hexylamine salt)Example 31 30-40 parts blown olive oil 1-10 parts 69-50 parts blownneats-foot oil 3 H I Example 38 CHrC=O-Cnaphtheny1 -50 parts olive oil10 parts sulfonated castor oil 20 parts mineral oil 10-15 parts oleicacid O=P=(OH)z.morpholine(l-hydroxy-l-naphthenyl-3Fmethyl-2-butene-l-phosphinate morpholine salt)99-10 parts neats-foot oil 55 5 parts I Example 32 11 1-10 parts 01: CH-C-naphthenyl l I 1 1 O OH /CzH4OCHa clohe Cna then p y .HN andN-(CzEh-OCHa): v 0=P=(OH)z.triethylamine O H OCH (Oyclohexyl naphthenylhydroxy methane phosphinate triethyl 2 4 a amine salt) a (Methylnaphthenyl hydroxy methane phosphinate di-beta- 99430 parts blown neat,sfoot on methoxy ethyl-trl-betaqgethoxy-gth gzmlne salt) ramp e Example33 55 ts i1 '70 parts water 5 sperm 0 15 parts water-soluble celluloseester par S 5 parts OH I OH t I naphthenyl" naphthenyl 7naDhthenyl--Cnaphthenyl I 0: =(OH)z.NH2CzH4 OC2H4QCzHs 0=P 0Na(Dlnaphthenyl hydroxy methane phosphlnate-beta-ethoxy-betaethoxyethylamlne salt) l 0 K 20 parts butyl naphthenate (Dinaphthenyl hydroxy,methane sodium potassium salt) 20 parts mineral oil 7 10 partssulfonated olive oil The particular method of application ofthe yarntreating compositions of our invention to the yarn will depend largelyupon the nature of the yarn and the use for which it is intended. Ingeneral, the compositions may be applied by any of the standardprocedures such as roll, wick, bath, or spray application. If the yarnis in continuous filament form, compositions may be applied just as theyarn emerges from the spinning cabinet, or while passing from package topackage. Likewise, the lubricant may be applied during twisting,winding, crepeing or similar operations. In the case of cut staplefibers, the compositions may be conveniently applied in the form of anemulsion bath or spray, preferably after any desired special treatmentof the yarn such as crimping or the like. In some cases, thelubricating, softening and anti-static agent may be added to thespinning solution from which the yarn is to be spun.

The amount of the compositions applied will, in general, depend upon thepurpose for which the yarn is to be used. For example, if the yarn is tobe employed for knitting,anywhere from -25%, based on the dry weight ofthe yarn, may be applied. On the other hand, if the yarn is intended forweaving, the amount will generally run from about 1-5%.

In each of the compositions given, the essential lubricating, softeningand anti-static component is a compound of the type indicated above.However, as illustrated by the specific examples, such compositions maycontain other lubricating, softening, or anti-static agents to augmentor supplement the effect of the primary ingredient and thus give thecompositions added or improved properties. Likewise, solvents,non-solvents, blending agents, co-solvents, emulsifying agents,dispersing agents and similar ingredients may be added as circumstancesmay require to adapt the compositions for specific uses. Similarly,various dyes or other coloring matter may be added to the compositionsin case it is desired to permanently or fugitively tint the yarnundergoing treatment.

Although in the above examples we have referred to compositionscontaining specific proportions of the various ingredients, the amountsemployed in any given case may vary widely the composition is intended.For example, if

it is desired to control the solvent, softening, or

other specific action of the conditioning agent per se or of any otheringredient, the amount thereof may be adjusted in accordance with thedesired action.

While we have found it convenient to describe our invention withparticular reference to the treatment of yarns composed of or containingorganic derivatives of cellulose, particularly cellulose acetate, theconditioning agent and compositions described herein are also applicableto the conditioning of many other types of cellulose derivative yarns,such as those composed of or containing cellulose propionate, cellulosebutyrate, cellulose acetate propionate, cellulose acetate butyrate, thecellulose ethers such as ethyl, methyl and benzyl celluloses, viscoseand cuprammonium cellulose, silk, wool, cotton and other natural andartificial materials.

The term yarn as used herein and in the claims is to be understood ascovering single filaments, a plurality of filaments associated in theform of roving, threads and the like, either of high or low twist,composite threads or yarns composed of a mixture of natural andartificial filaments, composite threads formed by twisting togetherindividual threads or strands of the same or different natural orartificial materials of the same or different deniers, creped or crimpedyarns, and crimped or uncrimped cut staple fibers produced from naturalor artificial filaments,'and spun yarn produced from such staple fibers.

The yarn conditioning methods and compositions of our invention possessmany outstanding advantages. The fundamental and distinguishingcharacteristic of the agents described herein is their ability tolubricate, soften and give valuable anti-static properties to yarns,particularly those composed of or containing organic derivatives ofcellulose such as cellulose acetate, and

to render them amenable to various textile operations. These agents areespecially valuable in the anti-static treatment of cellulose derivativecut staple fibers.

As indicated above, these compounds are distinguished by the fact thatthey have an especial solvent power for a wide variety of mineral, blownand unblown, drying and semi-drying animal and vegetable oils.Furthermore, due to their ready solubility in water, they may be removedfrom yarns and fabrics by means of the usual aqueous scour baths. Inaddition, their ability to emulsify various oils customarily used foryarn treatment makes them especially valuable for the preparation ofemulsions designed for use in the anti-static treatment of cut staplefibers.

What we claim is:

1. The process of conditioning yarn composed of or containing celluloseacetate to render it amenable to textile operations including knitting,weaving, spinning, carding, drawing and the like which comprisesapplying thereto prior to any textile operation thereon a lubricatingand antistatic composition containing as its essential lubricating andanti-static component diethylcyclohexylamine salt of phosphinatedstearylpalymityl xylyl ketone.

2. Textile yarns composed of or containing cellulose acetate amenable totextile operations including knitting, weaving, spinning, carding,drawing and the like, impregnated with a lubricating and anti-staticcomposition containing as its essential lubricating and anti-staticcomponent diethylcyclohexylamine salt of phosphinated stearyl-palmitylxylyl ketone.

3. A textile yarn conditioning agent for rendering yarns composed of orcontaining an organic derivative of cellulose more amenable, to textileoperations including knitting, weaving, spinning, carding, drawing andthe like, containing as its essential lubricating and anti-staticcomponent diethylcyclohexylamine salt of phosphinated stearyl-palmltylxylyl ketone.

JOSEPH B. DICKEY. JAMES G. MCNALLY.

